This review provides a comprehensive discussion on the microwave-assisted synthesis of various materials for photoluminescence and photocatalytic applications. In the past decade, because of its ability to synthesize nanomaterials through faster, cleaner and more cost-effective routes compared to conventional heating, microwave techniques have gained significant importance for the synthesis of metal oxides, fluorides, sulphides, and quantum dots. Additionally, due to the uniqueness of its heating mechanism, the synthesis of materials in various nanostructured forms through microwave-assisted methods has been of great interest and is widely pursued. The materials thus synthesized have been applied as sensing elements in gas sensors, luminescent nanoprobes in bioimaging, materials in fuel cells and solar cells and as photocatalysts for water treatment and energy harvesting. This review describes and discusses their optical and photocatalytic performance in detail, emphasizing on the reaction parameters employed and the structural and morphological properties obtained.